Phosphorous and chlorine-containing copolymers as lubricant additives



United States Patent Ofifice 3,227,696 Patented Jan. 4, 1906 PHOSPHOROUSAND CHLORINE-CONTAINING CGPOLYMERS AS LUBRICANT ADDITIVES Dervin L.Flowers, Redwood City, and Lyman E. Lorensen, Orinda, Calif., assignorsto Shell Oil Company, New York, N.Y., a corporation of Delaware NoDrawing. Original application Feb. 26, 1960, Ser. No. 11,139, now PatentNo. 3,151,078, dated Sept. 29, 1964. Divided and this application June29, 1964,

Ser. No. 379,017

3 Claims. (Cl. 260-805} This application is a division of copendingpatent application Serial No. 11,139 filed February 26, 1960, now U.S.P.3,151,078. 7

The invention relates to a new class of oil-soluble polypolar polymershaving a long linear hydrocarbon backbone chain having attached todifferent carbon atoms in the chain dissimilar polar groups one of whichis a phosphono-containing group and the other being a polar containingoil-solubilizing group. Novel copolymers of the present invention areuseful in improving hydrocarbon liquids with respect to detergent,extreme pressure, pour point depression, viscosity-temperature andanti-wear properties and the like.

It is an object of the invention to provide a new class of usefulpolymers and particularly oil-soluble polymers. It is a further objectto provide new polymers which are useful as multifunctional additivesfor liquid hydrocarbons such as lubricating oils and fuel compositions.

It has now been discovered that objects of the invention areaccomplished by the novel polymers having a plurality of recurringdissimilar units as represented by the following:

R R hat l an; l

wherein R is hydrogen or a C alkyl radical, or a halogen atom or anamino group, R is hydrogen, or a hydrocarbyl or halo-substitutedhydrocarbyl radical, e.g., alkyl, aryl, aralkyl, alkaryl or cycloalkylor halo derivatives thereof such as chloro or bromo alkyl radical havingfrom 1 to 18, preferably 2-8 carbon atoms, and Y is an oilsolubilizingradical containing a C alkyl radical (R) attached indirectly to thebackbone chain through a polar group such as 0 0 0 H [I ll ll I 0 R,ooR", --C-N-R" or the like, n is zero or 1 and m is a whole number. Themolecular weights of the polymers vary from about 5,000 to about amillion, preferably from 25,000 to 80,000.

The oil-soluble polymers having the above recurring dissimilar unitsshown in Formula I are prepared by copolymerizing (l) a monoolefinicallypolymerizable phosphonate monomer, such as a vinyl or allyl phosphonate,and (2) a polymerizable oleophilic long-chain alkyl ester or amide of analpha,beta-unsaturated acid such as an ester of amide of acrylic acid ormethacrylic acid or maleic anhydride or fumaric acid or ester of a lowerunsaturated alcohol, such as vinyl alcohol and allyl alcohol, and a longchain fatty acid or corresponding amide. The mole ratio of (1) to (2)can vary from 1:10 to 10:1, preferably 1:4 to 4:1, respectively.

The polymerizable phosphono monomers include mono or bis-(hydrocarbyl orhalohydrocarbyl)vinyl or allylphosphonat'es such as mono(ethyl)vinylacid phosphonate,

mono(butyl)vinyl acid phosphonate, mono(octyl)vinyl acid phosphonate,mono(cyclohexyl)vinyl acid phosphonate, mono(phenyl)vinyl acidphosphonate, mono (benzyl)vinyl acid phosphonate,mono(omega-chloroethyl)vinyl acid phosphonate, mono(omega-chlorobutyl)vinyl acid phosphonate, mono(omega-chlorooctyl)vinyl acid phosphonate,bis(ethyl)vinyl phosphonate, bis(butyl)vinyl phosphonate,bis(benzyl)vinyl phosphonate, bis(omega-chloroethyl)vinyl phosphonate,bis(ornegachlorobutyDvinyl phosphonate, bis(omega-chloroethyl) allylphosphonate, bis(benzyl)allyl phosphonate, bis (cy-clohexyl)allylphosphonate and mixtures thereof.

The other (non-phosphono) polymerizable monomer, containing oleophiliccomponents containing an aliphatic hydrocarbon chain of at least 8carbon atoms which is not part of the main hydrocarbon polymer chainincludes polymerizable esters, and/ or amides of unsaturated acids.Suitable esters include acrylic or alkacrylic esters of aliphaticalcohols of at least 8 carbon atoms, preferably of from 10 to 20 carbonatoms, and include, inter alia, decyl acrylate, lauryl acrylate, stearylacrylate, eicosanyl acrylate, docosanyl acrylate, decyl methacrylate,lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, and thelike, and mixtures thereof. Small amounts, not more than 20%, of themonomers just described such as C alkyl acrylates or methacrylates canbe replaced with lower C alkyl acrylates or methacrylates such as methylor butyl methacrylates in order to improve the viscosity temperatureproperties of the final copolymer of this invention.

Other substances include the vinyl esters of long-chain carboxylic acidssuch as vinyl laurate, vinyl palmitate, vinyl stearate, vinyl oleate andthe like and mixtures thereof; long-chain esters of vinylenedicarboxylic acids such as methyl lauryl fumarate; and methyl stearylmaleate, N-long chain hydrocarbon substituted amides of unsaturatedacids such as N-stearyl methacrylamide, N-lauryl methacrylamide,N-stearyl acrylamide and the like. These components can be employedalone or in various combinations. The technical lauryl methacrylateobtained from the commercial mixture of long-chain alcohols in the C toC range derived from coconut oil is an especially useful oleophiliccomponent of the copolymer. The group of acrylic and alkacrylic estersof ali phatic alcohols of at least eight carbon atoms are, in general,well suited as the oleophilic component of the copolymer.

The reaction temperature may vary from ambient temperature to 150 C. andthe reaction time may vary from a fraction of an hour to over 72 hoursuntil the reaction is complete.

The following examples are given as representative preparations ofpolymers of the invention.

Example I A mixture of lauryl methacrylate, stearyl methacrylate, methylmethacrylate and bis(fl-chloroethyl)vinyl phosphonate in the mol ratioof 3.2/2.2/3/1, respectively, was reacted in the presence of ditertbutylperoxide (0.30%) at C. for 24 hours. The unreacted monomers were removedby distillation. The recovered oilsoluble copolymer had a molecularweight of about 100,- 000. Analysis of the copolymer indicated molratios of the monomers entering into the polymer to be 3/ 2/ 3 /0.3,respectively.

Example 11 A mixture of vinyl stearate, vinyl laurate and bis( 8-chloroethyl)vinyl phosphonate in the mol ratio of 2/ 3/ 1, respectively,was reacted under the conditions of Example I. The recovered polymerproduct was oil-soluble and 3 had a molecular weight of about 200,000and the mol ratio of the reactants were 2/ 3/ 0.35.

Following the procedure of Examples I and II, other polymers wereprepared in accordance with the following We claim as our invention: 1.An oil-soluble copolymer of vinyl stearate and bis 3-chloroethyl)vinylphosphonate having a molecular weight of from about 25,000 to about800,000.

Bis(benzyl)vinyl phosphonate (1) Mono(fl-chloroethybvinyl phosphonate(1) Mono(ehloro-phenyl)vinyl phosphonate (1) l\lono(cyclohexyl)vinylphosphonate (l) tabulation: 5 2. An oil-soluble copolymer of vinylstearate, vinyl Example Catalyst Tgnp P-G Containing Monomer aOil-Solubillzing Monomers A III Beuzoyl peroxide 100Bis(6ch10r0ethyl)vinyl phosphonate (1) Allyl stearate (2). IVDitertbutyl peroxide 120 do N-stearyl methacrylarnide. V do 100 do Vinylstearate (1) B-stearyl methaerylate (1). 100 B s(bntyl)vmyl phosphonate(1) stearyl methacrylate (4). 100 B1s(8-ehloroethyl)allyl phosphonate(1)- Stearyl methacrylate (2).

Vinyl stearate (2).

Vinyl laurate (3).

Vinyl stearate (1) vinyl laurate (1).

a The figures in indicate the 11101 ratio of the starting monomer whichin the end product is essentially the same.

The novel polymers are effective as extreme pressure, anti-wear anddetergent additives in liquid hydrocarbon compositions such as minerallubricating oil in the range of from about 0.001% to about 10%,preferably from about 0.02% to about 5% by weight. The lubricating stockfor this purpose can be any natural or synthetic hydrocarbonaceousmaterial having lubricating properties. Thus, the base may be ahydrocarbon oil within a wide viscosity range, e .g., 100 SUS at 100 F.to 150 SUS at 210 F. The hydrocarbon oils may be blended with fixed oilssuch as castor oil, lard oil and the like,

and/or with synthetic lubricants such as polymerized olefins, copolymersof alkylene glycols and oxides; organic esters of polybasic organic andinorganic acids, e.g., (ii-2- ethylh'exyl sebacate, dioctyl phthalate,trioctyl phosphate; polymeric tetrahydrofuran; polyalkyl siliconepolymers, e.g., dimethyl silicone polymer and the like. In addition thebase can be gasoline, fuel oils or greases.

The outstanding properties of oil compositions of this invention weredemonstrated when a mineral lubricating oil containing 2% of additive ofExample I (Composition A) or 2% of additive of Example II (CompositionB) were found to have VI values of about 140 as compared to 92 for theneat oil and in the L-4 engine test Compositions A and B gave cleanengines with no evidence of wear or corrosion or sludge formation,whereas a comrnercial detergent oil containing a metallic detergent(sulfonate) tested under the same engine test conditions resulted insevere corrosion and sludge formation in th engine.

laurate and bis(fi-chloroethyl)vinyl phosphonate having a molecularweight of from about 25,000 to about 800,000. 3. An oil-solublecopolymer of a bis(w-chloroalkyl) vinyl phosphonate and at least onevinyl ester of a longchain fatty acid having from 8 to 20 carbon atoms.

References Cited by the Examiner umn 4132.

LEON J. BERCOVITZ, Primary Examiner.

CHARLES B. PARKER, FRANK M. SIKORA, RALPH A. WHITE, Assistant Examiners.

3. AN OIL-SOLUBLE COPOLYMER OF A BIS(W-CHLOROALKYL) VINYL PHOSPHONATEAND AT LEAST ONE VINYL ESTER OF A LONGCHAIN FATTY ACID HAVING FROM 8 TO20 CARBON ATOMS.